EP4253082A1 - Kautschukzusammensetzung für winterreifen und winterreifen - Google Patents

Kautschukzusammensetzung für winterreifen und winterreifen Download PDF

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Publication number
EP4253082A1
EP4253082A1 EP23162953.6A EP23162953A EP4253082A1 EP 4253082 A1 EP4253082 A1 EP 4253082A1 EP 23162953 A EP23162953 A EP 23162953A EP 4253082 A1 EP4253082 A1 EP 4253082A1
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EP
European Patent Office
Prior art keywords
phr
rubber composition
rubber
tire
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23162953.6A
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English (en)
French (fr)
Inventor
Luisa Fernanda MUNOZ MEJIA
Claude Charles Jacoby
Karmena Izabela Anyfantaki
Evangelia Konstantaki
Veronique HERBEUVAL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Goodyear Tire and Rubber Co
Original Assignee
Goodyear Tire and Rubber Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Goodyear Tire and Rubber Co filed Critical Goodyear Tire and Rubber Co
Publication of EP4253082A1 publication Critical patent/EP4253082A1/de
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present invention is directed to a rubber composition, in particular a sulfur curable or cured rubber composition, e.g., for a tire. Moreover, the present invention is directed to a rubber component comprising such a rubber composition as well as to a tire comprising said rubber composition and/or rubber component.
  • the invention relates to a rubber composition in accordance with claim 1 and to a tire in accordance with claim 13.
  • One object of the present invention is to provide a rubber composition that may be used with a winter tire for advanced performance on ice or on iced roads.
  • Another object of the present invention is to provide a rubber composition that may be used with a winter tire for improved rolling resistance.
  • Yet another object of the present invention may be to provide a winter tire with advanced performance on ice (e.g., grip) and advanced rolling resistance.
  • an object may be to provide at the same time good snow, wet and/or dry handling performance.
  • the present invention is directed to a rubber composition
  • a rubber composition comprising from 35 phr to 60 phr of a first polybutadiene rubber having a glass transition temperature within a range of -80°C to -105°C, from 5 phr to 30 phr of a second polybutadiene rubber having a glass transition temperature within a range of -20°C to -40°C, and 10 to 60 phr of polyisoprene selected from one or more of synthetic polyisoprene and natural rubber.
  • the rubber composition comprises from 30 phr to 200 phr of at least one filler, and from 40 phr to 120 phr of at least one plasticizer having a glass transition temperature within a range of -40°C to -110°C.
  • the rubber composition in accordance with the present invention combines three polymers, i.e., a low glass transition temperature polybutadiene rubber, a high glass transition temperature polybutadiene rubber and a polyisoprene, preferably a cis 1,4-polyisoprene (such as with a glass transition temperature between -60°C and -75°C), together with relatively high amounts of plasticizer within the claimed Tg range.
  • the compound according to the present invention provides good grip at very low temperatures and good hysteresis properties which translate into a limited rolling resistance of the tire.
  • the first polybutadiene rubber has a vinyl content of less than 25%, preferably less than 20%, or even more preferably less than 15%.
  • the first polybutadiene rubber has a vinyl content of at least 1%, optionally at least 5% or at least 10%. Such low vinyl ranges have been found to be most preferably.
  • the first polybutadiene rubber has a cis content of less than 60%, preferably less than 50% or even less than 40%.
  • the cis content is higher than 10% and preferably higher than 20% or 30%.
  • the first polybutadiene rubber is a low cis polybutadiene which has optionally been made with a n-butyl-lithium initiator.
  • the low cis content helps to avoid crystallization at low temperatures.
  • the first polybutadiene rubber has a weight average molecular weight Mw within a range of 250k g/mol to 450k g/mol. Mw is determined herein using gel permeation chromatography (GPC) according to ASTM 5296-11 using polystyrene calibration standards, or equivalent.
  • GPC gel permeation chromatography
  • the first polybutadiene rubber has a glass transition temperature of at most -80 °C, preferably of at most -85 °C, and/or of at least -99 °C, preferably of at least -95 °C.
  • the second polybutadiene rubber has a weight average molecular weight Mw within a range of 500k g/mol to 900k g/mol, preferably to 800k g/mol or 700k g/mol.
  • the second polybutadiene rubber has a vinyl content of more than 50%, preferably more than 60% or more than 70%.
  • the second poly butadiene rubber is a high vinyl polybutadiene rubber.
  • the second polybutadiene rubber has a glass transition temperature within of at least most -20°c and/or at least -35°C.
  • the rubber composition is free from styrene containing rubber, such as styrene butadiene rubber, or comprises less than 5 phr, preferably less than 1 phr of such rubber.
  • the rubber composition comprises more first polybutadiene rubber than polyisoprene, all by weight.
  • the rubber composition comprises at least 5% (by weight) more, or alternatively at least 2 phr more, of the first polybutadiene than polyisoprene.
  • the rubber composition comprises at most 20% (by weight) more, or alternatively at most 15 phr more, of the first polybutadiene than polyisoprene.
  • the rubber composition comprises more polyisoprene than second polybutadiene, all by weight.
  • the rubber composition comprises at least 5% (by weight) more, or alternatively at least 2 phr more, of the polyisoprene than of the second polybutadiene.
  • the rubber composition comprises at most 500% or 5 times (all by weight) more, or alternatively at most 40 phr more, of the polyisoprene than of the second polybutadiene.
  • the rubber composition comprises one or more of: from 10 to 20 phr of the second polybutadiene rubber, from 40 to 60 phr of the first polybutadiene rubber, from 30 to 50 phr said polyisoprene.
  • said polyisoprene is cis 1,4-polyisoprene, preferably synthetic cis 1,4-polyisoprene or natural rubber.
  • the filler comprises predominantly silica.
  • the rubber composition comprises 80 phr to 150 phr of silica, preferably from 80 phr to 140 phr silica, or even more preferably from 95 phr to 140 phr of silica or from 105 to 135 phr of silica.
  • said silica has a BET surface area within a range of 90 m 2 /g to 140 m 2 /g, preferably from 100 m 2 /g to 135 m 2 /g.
  • said plasticizer is a liquid plasticizer such as an oil or a liquid diene-based polymer.
  • Liquid plasticizer means herein that the plasticizer is liquid at 23°C.
  • said plasticizers comprise at least one oil having a glass transition temperature below -35°C.
  • the rubber composition comprises 55 phr to 95 phr of at least one liquid plasticizer having a glass transition temperature within a range of -40°C and - 100°C.
  • said liquid plasticizer comprises or consists of one or more oils.
  • a first oil has a glass transition temperature within a range of -40°C and -85°C and a second oil has a glass transition temperature within the range of - 90°C and -100°C.
  • the first oil is a mineral oil and/or the second oil is a triglyceride oil or vegetable oil.
  • the rubber composition comprises from 8 phf (parts by hundred parts of filler, all by weight) to 15 phf of at least one silane.
  • the first polybutadiene rubber is functionalized for the coupling to silica.
  • said first polybutadiene rubber is functionalized with at least one of an amino group, a siloxy group, and a silane group.
  • the first polybutadiene rubber comprises at least one functional group selected from one or more of: an amino siloxy group, an amino siloxane group, and an amino silane group.
  • said first polybutadiene rubber is end-chain functionalized with such groups.
  • the rubber composition may include at least one additional diene-based rubber.
  • Representative synthetic polymers may be the homopolymerization products of butadiene and its homologues and derivatives, for example, methylbutadiene, dimethylbutadiene and pentadiene as well as copolymers such as those formed from butadiene or its homologues or derivatives with other unsaturated monomers.
  • acetylenes for example, vinyl acetylene
  • olefins for example, isobutylene, which copolymerizes with isoprene to form butyl rubber
  • vinyl compounds for example, acrylic acid, acrylonitrile (which polymerize with butadiene to form NBR), methacrylic acid and styrene, the latter compound polymerizing with butadiene to form SBR, as well as vinyl esters and various unsaturated aldehydes, ketones and ethers, e.g., acrolein, methyl isopropenyl ketone and vinylethyl ether.
  • synthetic rubbers include neoprene (polychloroprene), polybutadiene (including cis 1,4-polybutadiene), polyisoprene (including cis 1,4-polyisoprene), butyl rubber, halobutyl rubber such as chlorobutyl rubber or bromobutyl rubber, styrene/isoprene/butadiene rubber, copolymers of 1,3-butadiene or isoprene with monomers such as styrene, acrylonitrile and methyl methacrylate, as well as ethylene/propylene terpolymers, also known as ethylene/propylene/diene monomer (EPDM), and in particular, ethylene/propylene/dicyclopentadiene terpolymers.
  • neoprene polychloroprene
  • polybutadiene including cis 1,4-polybutadiene
  • Rubbers which may be used include alkoxy-silyl end functionalized solution polymerized polymers (SBR, PBR, IBR and SIBR), silicon-coupled and tin-coupled star-branched polymers.
  • SBR alkoxy-silyl end functionalized solution polymerized polymers
  • PBR polybutadiene
  • SIBR silicon-coupled star-branched polymers
  • Preferred rubber or elastomers may be in general natural rubber, synthetic polyisoprene, polybutadiene and SBR including SSBR.
  • an emulsion polymerization derived styrene/butadiene might be used having a styrene content of 20 to 28 percent bound styrene or, for some applications, an ESBR having a medium to relatively high bound styrene content, namely, a bound styrene content of 30 to 45 percent. In many cases the ESBR will have a bound styrene content which is within the range of 26 percent to 31 percent.
  • emulsion polymerization prepared ESBR it may be meant that styrene and 1,3-butadiene are copolymerized as an aqueous emulsion. Such are well known to those skilled in such art.
  • the bound styrene content can vary, for example, from 5 to 50 percent.
  • the ESBR may also contain acrylonitrile to form a terpolymer rubber, as ESBAR, in amounts, for example, of 2 to 30 weight percent bound acrylonitrile in the terpolymer.
  • ESBAR acrylonitrile to form a terpolymer rubber
  • Emulsion polymerization prepared styrene/butadiene/acrylonitrile copolymer rubbers containing 2 to 40 weight percent bound acrylonitrile in the copolymer may also be contemplated as diene-based rubbers.
  • solution polymerization prepared SBR may be used.
  • Such an SSBR may for instance have a bound styrene content in a range of 5 to 50 percent, preferably 9 to 36, percent, and most preferably 26 to 31 percent.
  • the SSBR can be conveniently prepared, for example, by anionic polymerization in an inert organic solvent. More specifically, the SSBR can be synthesized by copolymerizing styrene and 1,3-butadiene monomer in a hydrocarbon solvent utilizing an organo lithium compound as the initiator.
  • the solution styrene butadiene rubber is a tin-coupled polymer.
  • the SSBR is functionalized for improved compatibility with silica.
  • the SSBR is thio-functionalized. This helps to improve stiffness of the compound and/or its hysteresis behavior.
  • the SSBR may be a thio-functionalized, tin-coupled solution polymerized copolymer of butadiene and styrene.
  • the rubber composition is free of any SBR, IBR and SIBR or comprises at least less than 5 phr of such rubbers.
  • a synthetic or natural polyisoprene rubber (natural rubber) may be used.
  • Synthetic cis-1,4 polyisoprene and natural rubber are as such well known to those having skill in the rubber art.
  • the cis 1,4-microstructure content may be at least 90% and is typically at least 95% or even higher.
  • cis-1,4 polybutadiene rubber (BR or PBD) is used.
  • Suitable polybutadiene rubbers may be prepared, for example, by organic solution polymerization of 1,3-butadiene.
  • the BR may be conveniently characterized, for example, by having at least a 90 percent cis-1,4-microstructure content ("high cis” content) and a glass transition temperature (Tg) in a range of from -95 to -110°C.
  • Suitable polybutadiene rubbers are available commercially, such as Budene ® 1207, Budene ® 1208, Budene ® 1223, or Budene ® 1280 from The Goodyear Tire & Rubber Company.
  • These high cis-1,4-polybutadiene rubbers can for instance be synthesized utilizing nickel catalyst systems which include a mixture of (1) an organonickel compound, (2) an organoaluminum compound, and (3) a fluorine containing compound as described in United States Patent 5,698,643 and United States Patent 5,451,646 , which are incorporated herein by reference.
  • a glass transition temperature, or Tg, of an elastomer represents the glass transition temperature of the respective elastomer in its uncured state.
  • a glass transition temperature of an elastomer composition represents the glass transition temperature of the elastomer composition in its cured state.
  • a Tg is determined as a peak midpoint by a differential scanning calorimeter (DSC) at a temperature rate of increase of 20°C per minute, according to ASTM D3418 or equivalent.
  • phr refers to "parts by weight of a respective material per 100 parts by weight of rubber, or elastomer".
  • a rubber composition is comprised of 100 parts by weight of rubber/elastomer.
  • the claimed composition may comprise other rubbers / elastomers than explicitly mentioned in the claims, provided that the phr value of the claimed rubbers / elastomers is in accordance with claimed phr ranges and the amount of all rubbers / elastomers in the composition results in total in 100 parts of rubber.
  • the composition may further comprise from 1 phr to 10 phr, optionally from 1 to 5 phr, of one or more additional diene-based rubbers, such as SBR, SSBR, ESBR.
  • the composition may include less than 5 phr, preferably less than 3, phr of an additional diene-based rubber or be also essentially free of such an additional diene-based rubber.
  • compound and “composition” and “formulation” may be used herein interchangeably, unless indicated otherwise.
  • the terms “rubber” and “elastomer” may also be used herein interchangeably.
  • the rubber composition includes from 1 phr to 80 phr, or from 5 phr to 80 phr, of a resin, preferably having a glass transition temperature Tg greater than 20 °C.
  • a Tg for resins is determined as a peak midpoint by a differential scanning calorimeter (DSC) at a temperature rate of increase of 10 °C per minute, according to ASTM D6604 or equivalent.
  • the resin has a softening point above 70 °C as determined by ASTM E28 which might sometimes be referred to as a ring and ball softening point.
  • the rubber composition includes from 10 phr to 60 phr or from 20 phr to 60 phr or from 30 phr to 60 phr of resin.
  • the resin is selected from the group consisting of coumarone-indene resin, petroleum hydrocarbon resin, terpene polymers/resins, styrene/alphamethylstyrene resins, terpene phenol resin, rosin derived resins and copolymers and/or mixtures thereof.
  • a coumarone-indene resin preferably contains coumarone and indene as monomer components making up the resin skeleton (main chain).
  • Monomer ingredients other than coumarone and indene which may be incorporated into the skeleton are, for example, methyl coumarone, styrene, alphamethylstyrene, methylindene, vinyltoluene, dicyclopentadiene, cyclopentadiene, and diolefins such as isoprene and piperlyene.
  • Coumarone-indene resins have preferably melting points ranging from 10 °C to 160° C (as measured by the ball-and-ring method). Even more preferably, the melting point ranges from 30 to 100° C.
  • Suitable petroleum resins include both aromatic and nonaromatic types. Several types of petroleum resins are available. Some resins have a low degree of unsaturation and high aromatic content, whereas some are highly unsaturated and yet some contain no aromatic structure at all. Differences in the resins are largely due to the olefins in the feedstock from which the resins are derived.
  • Conventional derivatives in such resins include any C5 species (olefins and diolefines containing an average of five carbon atoms) such as cyclopentadiene, dicyclopentadiene, diolefins such as isoprene and piperylene, and any C9 species (olefins and diolefins containing an average of 9 carbon atoms) such as vinyltoluene, alphamethylstyrene and indene.
  • Such resins are made by any mixture formed from C5 and C9 species mentioned above, and are known as C5/C9 copolymer resins. Petroleum resins are typically available with softening points ranging from 10° C. to 120° C. Preferably, the softening point ranges from 30 to 100° C.
  • C5 resins are aliphatic resins made from one or more of the following monomers: 1,3-pentadiene (e.g., cis or trans), 2-methyl-2-butene, cyclopentene, cyclopentadiene, and dicyclopentadiene.
  • a C9 resin is a resin made from one or more aromatic monomers, preferably chosen from the group of indene, methylindene, vinyl toluene, styrene and methylstyrene (such as alpha-methylstyrene).
  • a C9 modified resin is a resin (such as a C5 resin) which has been modified or functionalized with one or more aromatic monomers, preferably chosen from the group of indene, methylindene, vinyl toluene, styrene and methylstyrene (such as alpha methylstyrene).
  • Terpene resins are preferably comprised of polymers of at least one of limonene, alpha pinene, beta pinene and delta-3-carene. Such resins are available with melting points ranging from 10° C to 135° C.
  • Terpene-phenol resins may be derived by copolymerization of phenolic monomers with terpenes such as limonenes, pinenes and delta-3-carene.
  • resins derived from rosins and derivatives thereof are, for example, gum rosin, wood rosin and tall oil rosin. Gum rosin, wood rosin and tall oil rosin have similar compositions, although the amount of components of the rosins may vary. Such resins may be dimerized, polymerized or disproportionated. Such resins may be in the form of esters of rosin acids and polyols such as pentaerythritol or glycol.
  • a styrene/alphamethylstyrene resin is considered herein to be a (preferably relatively short chain) copolymer of styrene and alphamethylstyrene with a styrene/alphamethylstyrene molar ratio in a range of about 0.05 to about 1.50.
  • a resin can be suitably prepared, for example, by cationic copolymerization of styrene and alphamethylstyrene in a hydrocarbon solvent.
  • the contemplated styrene/alphamethylstyrene resin can be characterized, for example, by its chemical structure, namely, its styrene and alphamethylstyrene contents and by its glass transition temperature, molecular weight and molecular weight distribution.
  • said resin may be partially or fully hydrogenated.
  • the rubber composition is resin free or comprises less than 5 phr of resin or less than 3 phr of resin, in particular hydrocarbon resin.
  • the rubber composition includes oil, in particular processing oil.
  • Processing oil may be included in the rubber composition as extending oil typically used to extend elastomers. Processing oil may also be included in the rubber composition by addition of the oil directly during rubber compounding.
  • the processing oil used may include both extending oil present in the elastomers, and process oil added during compounding.
  • Suitable process oils may include various oils as are known in the art, including aromatic, paraffinic, naphthenic, vegetable oils, and low PCA oils, such as MES, TDAE, SRAE and heavy naphthenic oils.
  • Suitable low PCA oils may include those having a polycyclic aromatic content of less than 3 percent by weight as determined by the IP346 method.
  • IP346 Procedures for the IP346 method may be found in Standard Methods for Analysis & Testing of Petroleum and Related Products and British Standard 2000 Parts, 2003, 62nd edition, published by the Institute of Petroleum, United Kingdom .
  • vegetable oils that can be used include soybean oil, sunflower oil, canola (rapeseed) oil, corn oil, coconut oil, cottonseed oil, olive oil, palm oil, peanut oil, and safflower oil. Soybean oil and corn oil are typically preferred vegetable oils.
  • a glass transition temperature Tg for liquid plasticizers, such as oil, is determined as a peak midpoint by a differential scanning calorimeter (DSC) at a temperature rate of increase of 10°C per minute, according to ASTM E1356 or equivalent.
  • DSC differential scanning calorimeter
  • the rubber composition includes silica.
  • siliceous pigments which may be used in the rubber compound include for instance conventional pyrogenic and precipitated siliceous pigments (silica).
  • precipitated silica is used.
  • the conventional siliceous pigments may be precipitated silicas such as, for example, those obtained by the acidification of a soluble silicate, e.g., sodium silicate.
  • Silicas might be characterized, for example, by having a BET surface area, as measured using nitrogen gas. In one embodiment, the BET surface area may be in the range of 40 to 600 square meters per gram. In another embodiment, the BET surface area may be in a range of 50 to 300 square meters per gram.
  • the BET surface area is determined according to ASTM D6556 or equivalent and is described in the Journal of the American Chemical Society, Volume 60, Page 304 (1930 ).
  • the conventional silica may also be characterized by having a dibutylphthalate (DBP) absorption value in a range of 100 cm 3 /100g to 400 cm 3 /100g, alternatively 150 cm 3 /100g to 300 cm 3 /100g which is determined according to ASTM D 2414 or equivalent.
  • DBP dibutylphthalate
  • a conventional silica might be expected to have an average ultimate particle size, for example, in the range of 0.01 to 0.05 micron as determined by the electron microscope, although the silica particles may be even smaller, or possibly larger, in size.
  • silicas such as, only for example herein, and without limitation, silicas commercially available from PPG Industries under the Hi-Sil trademark with designations 210, 315G, EZ160G, etc.; silicas available from Solvay, with, for example, designations of Z1165MP and Premium200MP, and silicas available from Evonik AG with, for example, designations VN2 and Ultrasil 6000GR, 9100GR.
  • the rubber composition may comprise pre-silanized and/or precipitated silica.
  • pre-silanized, or in other words pre-hydrophobated, precipitated silica utilized is hydrophobated prior to its addition to the rubber composition by treatment with at least one silane.
  • Suitable silanes include but are not limited to alkylsilanes, alkoxysilanes, organoalkoxysilyl polysulfides and organomercaptoalkoxysilanes.
  • the pre-hydrophobated precipitated silica may be pre-treated with a silica coupling agent comprised of, for example, an alkoxyorganomercaptoalkoxysilane or combination of alkoxysilane and organomercaptoalkoxysilane prior to blending the pre-treated silica with the rubber instead of reacting the precipitated silica with the silica coupling agent in situ within the rubber.
  • a silica coupling agent comprised of, for example, an alkoxyorganomercaptoalkoxysilane or combination of alkoxysilane and organomercaptoalkoxysilane
  • said pre-silanized precipitated silica is precipitated silica pre-reacted with a silica coupler comprised of bis(3-triethoxysilylpropyl)polysulfide containing an average of from 1 to 5 connecting sulfur atoms (preferably 2 to 4) in its polysulfidic bridge or an alkoxyorganomercaptosilane.
  • a silica coupler comprised of bis(3-triethoxysilylpropyl)polysulfide containing an average of from 1 to 5 connecting sulfur atoms (preferably 2 to 4) in its polysulfidic bridge or an alkoxyorganomercaptosilane.
  • the rubber composition includes carbon black.
  • carbon blacks include N110, N121, N134, N220, N231, N234, N242, N293, N299, N315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991 grades.
  • These carbon blacks have iodine absorptions ranging from 9 to 145 g/kg and a DBP number ranging from 34 to 150 cm3/100 g. Iodine absorption values is determined according to ASTM D1510 or equivalent.
  • carbon black is used herein in amounts from 0.1 to 10 phr, ore 0.1 phr to 6 phr.
  • the rubber composition may contain sulfur containing organosilicon compounds or silanes.
  • suitable sulfur containing organosilicon compounds are of the formula: Z - Alk - Sn - Alk - Z I in which Z is selected from the group consisting of where R1 is an alkyl group of 1 to 4 carbon atoms, cyclohexyl or phenyl; R2 is an alkoxy of 1 to 8 carbon atoms, or cycloalkoxy of 5 to 8 carbon atoms; Alk is a divalent hydrocarbon of 1 to 18 carbon atoms and n is an integer of 2 to 8.
  • the sulfur containing organosilicon compounds are the 3,3'-bis(trimethoxy or triethoxy silylpropyl) polysulfides. In one embodiment, the sulfur containing organosilicon compounds are 3,3'-bis(triethoxysilylpropyl) disulfide and/or 3,3'-bis(triethoxysilylpropyl) tetrasulfide. Therefore, as to formula I, Z may be where R2 is an alkoxy of 2 to 4 carbon atoms, alternatively 2 carbon atoms; Alk is a divalent hydrocarbon of 2 to 4 carbon atoms, alternatively with 3 carbon atoms; and n is an integer of from 2 to 5, alternatively 2 or 4.
  • suitable sulfur containing organosilicon compounds include compounds disclosed in United States Patent 6,608,125 .
  • suitable sulfur containing organosilicon compounds include those disclosed in United States Patent Application Publication No. 2003/0130535 .
  • the sulfur containing organosilicon compound is Si-363 from Degussa.
  • the amount of the sulfur containing organosilicon compound in a rubber composition may vary depending on the level of other additives that are used. Generally speaking, the amount of the compound may range from 0.5 phr to 20 phr. Other preferred amounts are described herein above.
  • the rubber composition may be compounded by methods generally known in the rubber compounding art, such as mixing the various sulfur-vulcanizable constituent rubbers with various commonly used additive materials such as, for example, sulfur donors, curing aids, such as activators and retarders and processing additives, such as oils, resins including tackifying resins and plasticizers, fillers, pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozonants and peptizing agents.
  • additives mentioned above are selected and commonly used in conventional amounts.
  • sulfur donors include elemental sulfur (free sulfur), an amine disulfide, polymeric polysulfide and sulfur olefin adducts.
  • the sulfur-vulcanizing agent is elemental sulfur.
  • the sulfur-vulcanizing agent may for instance be used in an amount ranging from 0.5 phr to 8 phr, alternatively within a range of 1.5 phr to 6 phr.
  • Typical amounts of tackifier resins, if used, comprise for example 0.5 phr to 10 phr, usually 1 phr to 5 phr.
  • processing aids if used, comprise for example 1 phr to 50 phr (this may comprise in particular oil).
  • Typical amounts of antioxidants may for example comprise 1 phr to 5 phr.
  • Representative antioxidants may be, for example, diphenyl-p-phenylenediamine and others, such as, for example, those disclosed in The Vanderbilt Rubber Handbook (1978), Pages 344 through 346 .
  • Typical amounts of antiozonants, if used may for instance comprise 1 phr to 5 phr.
  • Typical amounts of fatty acids, if used, which can include stearic acid may for instance comprise 0.5 phr to 3 phr.
  • Typical amounts of waxes if used, may for example comprise 1 phr to 5 phr. Often microcrystalline waxes are used.
  • Typical amounts of peptizers may for instance comprise 0.1 phr to 1 phr.
  • Typical peptizers may be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide.
  • Accelerators may be preferably but not necessarily used to control the time and/or temperature required for vulcanization and to improve the properties of the vulcanizate.
  • a single accelerator system may be used, i.e., primary accelerator.
  • the primary accelerator(s) may be used in total amounts ranging from 0.5 phr to 4 phr, alternatively 0.8 phr to 1.5 phr.
  • combinations of a primary and a secondary accelerator might be used with the secondary accelerator being used in smaller amounts, such as from 0.05 phr to 3 phr, in order to activate and to improve the properties of the vulcanizate.
  • accelerators might be expected to produce a synergistic effect on the final properties and are somewhat better than those produced by use of either accelerator alone.
  • delayed action accelerators may be used which are not affected by normal processing temperatures but produce a satisfactory cure at ordinary vulcanization temperatures.
  • Vulcanization retarders might also be used.
  • Suitable types of accelerators that may be used in the present invention are for instance amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates.
  • the primary accelerator is a sulfenamide.
  • the secondary accelerator may be for instance a guanidine, dithiocarbamate or thiuram compound.
  • Suitable guanidines include dipheynylguanidine and the like.
  • Suitable thiurams include tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetrabenzylthiuram disulfide.
  • the mixing of the rubber composition can be accomplished by methods known to those having skill in the rubber mixing art.
  • the ingredients may be typically mixed in at least two stages, namely, at least one nonproductive stage followed by a productive mix stage.
  • the final curatives including sulfur-vulcanizing agents may be typically mixed in the final stage which is conventionally called the "productive" mix stage in which the mixing typically occurs at a temperature, or ultimate temperature, lower than the mix temperature(s) of the preceding nonproductive mix stage(s).
  • the terms "nonproductive" and “productive” mix stages are well known to those having skill in the rubber mixing art.
  • the rubber composition may be subjected to a thermomechanical mixing step.
  • the thermomechanical mixing step generally comprises a mechanical working in a mixer or extruder for a period of time, for example suitable to produce a rubber temperature between 140°C and 190°C.
  • the appropriate duration of the thermomechanical working varies as a function of the operating conditions, and the volume and nature of the components.
  • the thermomechanical working may be from 1 to 20 minutes.
  • the rubber composition may be incorporated in a variety of rubber components of the tire (or in other words tire components).
  • the rubber component may be a tread (including preferably a tread cap and/or a tread base), sidewall, apex, chafer, sidewall insert, wirecoat or innerliner.
  • Vulcanization of the pneumatic tire of the present invention may for instance be carried out at conventional temperatures ranging from 100°C to 200°C. In one embodiment, the vulcanization is conducted at temperatures which are within a range of 110°C to 180°C. Any of the usual vulcanization processes may be used such as heating in a press or mold, heating with superheated steam or hot air. Such tires can be built, shaped, molded and cured by various methods which are known and will be readily apparent to those having skill in such art.
  • the present invention is directed to a tire comprising the rubber composition according to the first aspect of the invention and optionally one or more of its embodiments.
  • the tire of the present invention may for example be a pneumatic tire or nonpneumatic tire, a race tire, a passenger tire, an aircraft tire, an agricultural tire, an earthmover tire, an off-the-road (OTR) tire, a truck tire, or a motorcycle tire.
  • the tire may also be a radial or bias tire.
  • said tire is a winter tire.
  • said tire is a winter tire and/or a tire having on its sidewall the 3 peak mountain snowflake symbol (3PMSF symbol).
  • said the rubber composition is comprised in a tread of the tire.
  • the rubber composition is provided in a radially outermost layer of the tread (contacting the road when driving).
  • the rubber composition of the Inventive Example provides improved ice performance and rolling resistance at the same time. Snow performance, wet braking performance and/or dry breaking performance remain almost unchanged versus the Comparative Example. Thus, the respective winter tire is particularly suitable for the efficient use in regions facing frequently icy roads.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP23162953.6A 2022-03-28 2023-03-20 Kautschukzusammensetzung für winterreifen und winterreifen Pending EP4253082A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202263324314P 2022-03-28 2022-03-28
US18/065,763 US20230303809A1 (en) 2022-03-28 2022-12-14 Rubber composition for a winter tire and a winter tire

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EP4253082A1 true EP4253082A1 (de) 2023-10-04

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4485205A (en) * 1980-02-08 1984-11-27 Tatsuo Fujimaki Rubber compositions suitable for tires comprising amorphous styrene-butadiene copolymer
US5451646A (en) 1994-12-05 1995-09-19 The Goodyear Tire & Rubber Company Technique for reducing the molecular weight and improving the processability of cis-1,4-polybutadiene
US5698643A (en) 1982-04-26 1997-12-16 The Goodyear Tire & Rubber Company Controlling the molecular weight of polybutadiene
US20030130535A1 (en) 2001-08-06 2003-07-10 Degussa Ag, Organosilicon compounds
US6608125B2 (en) 1997-08-21 2003-08-19 Crompton Corporation Blocked mercaptosilane coupling agents for filled rubbers
US7214731B2 (en) 2003-03-17 2007-05-08 The Goodyear Tire & Rubber Company Tire with low hydrocarbon emission rubber combination of tread and sidewall components with compositional limitations
EP3170679A1 (de) * 2015-11-18 2017-05-24 The Goodyear Tire & Rubber Company Gummizusammensetzung und reifen mit lauffläche für niedrigtemperaturleistung und nasstraktion
EP3913018A1 (de) * 2020-05-13 2021-11-24 The Goodyear Tire & Rubber Company Kautschukzusammensetzung und luftreifen

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4485205A (en) * 1980-02-08 1984-11-27 Tatsuo Fujimaki Rubber compositions suitable for tires comprising amorphous styrene-butadiene copolymer
US5698643A (en) 1982-04-26 1997-12-16 The Goodyear Tire & Rubber Company Controlling the molecular weight of polybutadiene
US5451646A (en) 1994-12-05 1995-09-19 The Goodyear Tire & Rubber Company Technique for reducing the molecular weight and improving the processability of cis-1,4-polybutadiene
US6608125B2 (en) 1997-08-21 2003-08-19 Crompton Corporation Blocked mercaptosilane coupling agents for filled rubbers
US20030130535A1 (en) 2001-08-06 2003-07-10 Degussa Ag, Organosilicon compounds
US7214731B2 (en) 2003-03-17 2007-05-08 The Goodyear Tire & Rubber Company Tire with low hydrocarbon emission rubber combination of tread and sidewall components with compositional limitations
EP3170679A1 (de) * 2015-11-18 2017-05-24 The Goodyear Tire & Rubber Company Gummizusammensetzung und reifen mit lauffläche für niedrigtemperaturleistung und nasstraktion
EP3913018A1 (de) * 2020-05-13 2021-11-24 The Goodyear Tire & Rubber Company Kautschukzusammensetzung und luftreifen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 60, 1930, pages 304

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